US9272462B2 - Minute convexo-concave pattern forming method and forming device, and transfer substrate producing method and transfer substrate - Google Patents

Minute convexo-concave pattern forming method and forming device, and transfer substrate producing method and transfer substrate Download PDF

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Publication number
US9272462B2
US9272462B2 US13/636,253 US201113636253A US9272462B2 US 9272462 B2 US9272462 B2 US 9272462B2 US 201113636253 A US201113636253 A US 201113636253A US 9272462 B2 US9272462 B2 US 9272462B2
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Prior art keywords
transfer substrate
mold
concave pattern
peeling
substrate
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US20130207309A1 (en
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Shinichiro Okada
Shotaro Ogawa
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Fujifilm Corp
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Fujifilm Corp
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C59/00—Surface shaping of articles, e.g. embossing; Apparatus therefor
    • B29C59/002—Component parts, details or accessories; Auxiliary operations
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C33/00—Moulds or cores; Details thereof or accessories therefor
    • B29C33/42—Moulds or cores; Details thereof or accessories therefor characterised by the shape of the moulding surface, e.g. ribs or grooves
    • B29C33/424—Moulding surfaces provided with means for marking or patterning
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C33/00—Moulds or cores; Details thereof or accessories therefor
    • B29C33/44—Moulds or cores; Details thereof or accessories therefor with means for, or specially constructed to facilitate, the removal of articles, e.g. of undercut articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y10/00—Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0002—Lithographic processes using patterning methods other than those involving the exposure to radiation, e.g. by stamping
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
    • H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
    • H01L21/0273—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers characterised by the treatment of photoresist layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C33/00—Moulds or cores; Details thereof or accessories therefor
    • B29C33/42—Moulds or cores; Details thereof or accessories therefor characterised by the shape of the moulding surface, e.g. ribs or grooves
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
    • H01L21/683—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping
    • H01L21/6838—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping with gripping and holding devices using a vacuum; Bernoulli devices
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T156/00—Adhesive bonding and miscellaneous chemical manufacture
    • Y10T156/11—Methods of delaminating, per se; i.e., separating at bonding face
    • Y10T156/1168—Gripping and pulling work apart during delaminating
    • Y10T156/1195—Delaminating from release surface
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T156/00—Adhesive bonding and miscellaneous chemical manufacture
    • Y10T156/19—Delaminating means
    • Y10T156/1928—Differential fluid pressure delaminating means
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T156/00—Adhesive bonding and miscellaneous chemical manufacture
    • Y10T156/19—Delaminating means
    • Y10T156/1994—Means for delaminating from release surface

Definitions

  • the present invention relates to a minute convexo-concave pattern forming method and forming device, and transfer substrate manufacturing method and transfer substrate and, in particular, to a peeling technology for peeling a resist layer after transfer from a mold without damaging a minute convexo-concave pattern.
  • a nano imprint technology has attracted attention, in which a minute convexo-concave pattern in a nano size is formed on a substrate by using a polymer as a material to manufacture a high-functionality device such as a semiconductor, a recording medium, or an optical element.
  • a nano imprint scheme is a method of pressing a substrate coated with a resist (a resin material) onto a mold (a form) having a minute convexo-concave pattern formed thereon by electron beam exposure to transfer the minute convexo-concave pattern of the mold to a resist layer.
  • the nano imprint technology has features such that apparatus cost by microfabrication is inexpensive compared with the EUV scheme or the like and minute convexo-concave pattern shape in a size of several tens of nanometers can be transferred.
  • the nano imprint technology has a faulty peel problem in which when the resist layer and the mold are peeled after a minute convexo-concave pattern is transferred to the resist layer on the substrate, the minute convexo-concave pattern transferred to the resist layer tends to be damaged.
  • the nano imprint technology includes a transferring process of bringing the mold and the resist layer into contact with each other to form a minute convexo-concave pattern, and the faulty peel problem is a fundamental problem unavoidable due to the transferring process mentioned above.
  • PTL 1 discloses a pattern forming method in which an angle formed between a direction of a line of a convexo-concave pattern and a mold peeling direction is adjusted to prevent the convexo-concave pattern from being damaged at the time of peeling.
  • PTL 2 describes a method of forming a sufficient deformation adjacently to the mold so as to produce a resilient force larger than a bonding force between an imprinting material and the mold. This is thought to improve an imprinting method for use in a contact lithography process.
  • PTL 3 discloses a device manufacturing method in which, with the mold and the resin being in contact with each other, a state from the time when the mold starts moving in a direction of going away from the resin to the time of peeling is divided into a first state and a second state and a load change ratio acted between the mold and resin in the second state is set smaller than that in the first state. With this, it is thought to be able to achieve a high-speed releasing process and an excellent throughput.
  • the present invention was made in view of these circumstances, and has an object of providing a minute convexo-concave pattern forming method and forming device, and transfer substrate manufacturing method and transfer substrate allowing formation of a highly-accurate minute convexo-concave pattern even in a nano size because the minute convexo-concave pattern transferred to the resist layer of the transfer substrate can be effectively prevented from being damaged when the mold on a side of transferring the minute convexo-concave pattern and the transfer substrate on a transferred side are peeled.
  • a minute convexo-concave pattern forming method includes: a transferring step of transferring a minute convexo-concave pattern of a mold to a resist layer of a transfer substrate where the resist layer is formed on the substrate and curing the transferred minute convexo-concave pattern; and a peeling step of peeling the transfer substrate and the mold after curing the transferred minute convexo-concave pattern, and the peeling step includes: a first peeling step of pressurizing a substrate back surface side of the transfer substrate with a peripheral part of the transfer substrate being fixed to bend the transfer substrate in a curved shape and starting peeling of the transfer substrate and the mold with the bending of the transfer substrate; and a second peeling step of peeling a part of the minute convexo-concave pattern of the transfer substrate not peeled in the first peeling step by gradually decreasing a pressure for a pressurization so as to undo bending of the transfer substrate
  • the minute convexo-concave pattern forming method in accordance with the first aspect in the first peeling step, by pressurizing the substrate back surface side with the peripheral part of the transfer substrate being fixed to bend the transfer substrate in a curved shape, at a mold outer peripheral end, a peel angle with respect to the mold can be provided to the transfer substrate. With this, the minute convexo-concave pattern on the outer peripheral part of the transfer substrate is first peeled by using the bending.
  • the pressure for the pressurization on the substrate back surface side is gradually decreased to act a bending resilient force on the transfer substrate.
  • a peel force is provided toward a center part of the transfer substrate so that the transfer substrate bent in a curved shape becomes in a flat plate shape, and therefore the minute convexo-concave pattern of the center part of the transfer substrate not peeled in the first peeling step is peeled.
  • the pressurizing force is larger than the bending resilient force at this stage, and therefore bending increases.
  • the minute convexo-concave pattern of the outer peripheral part of the transfer substrate is peeled (the first peeling step).
  • the pressurizing force is gradually decreased, and when the bending resilient force becomes larger than the pressurizing force, the bending decreases and the substrate goes in a direction in which the bending is undone.
  • the minute convexo-concave pattern of the center part of the transfer substrate not peeled in the first peeling step is peeled (the second peeling step).
  • the minute convexo-concave pattern of a peel final end (a center of the transfer substrate) is coupled to the mold. Therefore, if a large bending resilient force (peel force) is provided at a dash when peeling is completed, the minute convexo-concave pattern of the peel final end may be broken or deformed.
  • the pressure for the pressurization on the transfer substrate is gradually decreased to gradually act the bending resilient force (peel force) on the transfer substrate, thereby peeling with a small peel force at a slow peeling speed.
  • peeling force the bending resilient force
  • the transfer substrate in the first peeling step, is preferably bent to an amount less than a maximum bending amount (a second aspect).
  • a second aspect the minute convexo-concave pattern at the peel final end where the minute convexo-concave pattern tends to be damaged can be peeled in the second peeling step capable of peeling with a small peel force at a slow peeling speed.
  • the maximum bending amount refers to a bending amount of the transfer substrate when a pressurizing force is applied in the state of a transfer substrate carrier.
  • the conditions are such that a bending amount is provided so that the minute convexo-concave pattern formed on the outer peripheral part of the transfer substrate can be peeled from the mold with the bending of the transfer substrate and, when a bending resilient force is acted on the transfer substrate, the entire minute convexo-concave pattern formed on the center part of the transfer substrate can be peeled from the mold with the bending resilient force.
  • the mold in the first peeling step, is preferably moved according to the bending of the transfer substrate in a direction in which the mold goes away from the transfer substrate (a third aspect).
  • the mold may be slid so as to follow the bending force of the transfer substrate, or the mold may be forcibly moved by a driving device by a predetermined amount.
  • the peel force by bending can be uniformly applied to the transfer substrate, and therefore the minute convexo-concave pattern of the outer peripheral part of the transfer substrate can be uniformly applied.
  • the bending of the transfer substrate by pressurizing on the substrate back surface side can be assisted, thereby achieving smooth bending.
  • a pressurizing force on the substrate back surface side is preferably gradually decreased, with the mold being fixed so as not to move (a fourth aspect).
  • the pressurizing force on the substrate back surface side is preferably gradually decreased while the mold is being moved in the direction in which the mold goes away from the transfer substrate continuously from the movement in the first peeling step (a fifth aspect).
  • the movement of the mold is preferably extremely slow at 0.1 mm/second or less.
  • the mold in the second peeling step, is preferably peeled with a pressurizing pressure on the substrate back surface side being kept, while the mold is being moved in the direction in which the mold goes away from the transfer substrate continuously from the movement in the first peeling step (a sixth aspect).
  • a load applied to the transfer substrate is preferably measured, and the pressurizing force is preferably controlled based on the measured load (a seventh aspect). With this, peeling can be performed while the peel force is accurately grasped.
  • a method of controlling the pressure for pressurization on the substrate back surface side without using a load cell there are a case of controlling based on an elapsed time from the start of the pressurization (an eighth aspect), a case of controlling based on a movement amount of the mold from the start of the pressurization (a ninth aspect), and a case of controlling based on a bending amount of the transfer substrate from the start of the pressurization (a tenth embodiment).
  • a minute convexo-concave pattern forming apparatus includes a peeling device which, after transferring and curing a minute convexo-concave pattern of a mold to a resist layer of a transfer substrate where a resist layer is formed on the substrate, peels the transfer substrate and the mold, and the peeling device includes: a peripheral part fixing member which fixes a peripheral part of the transfer substrate; a pressurizing part which pressurizes a substrate back surface side of the transfer substrate with the peripheral part of the transfer substrate being fixed to bend the transfer substrate in a curved shape; and a pressure control part which gradually decreases a pressure for a pressurization so as to undo the bending of the transfer substrate.
  • the present invention is configured as an apparatus.
  • the minute convexo-concave pattern forming apparatus preferably includes a moving and driving part which moves the mold in a direction in which the mold goes away from the transfer substrate (a twelfth aspect).
  • a moving and driving part which moves the mold in a direction in which the mold goes away from the transfer substrate.
  • the moving and driving part preferably includes a lock mechanism which locks the movement of the mold (a thirteenth aspect).
  • a load sensor which measures a load applied to the transfer substrate is preferably provided (a fourteenth aspect).
  • the minute convexo-concave pattern of the mold is transferred to the transfer substrate, and then the mold is peeled away from the transfer substrate.
  • a transfer substrate of a sixteenth aspect of the present invention is manufactured by using the minute convexo-concave pattern forming method according to any one of the first to tenth aspects to peel the minute convexo-concave pattern.
  • the transfer substrate described above is manufactured by using the minute convexo-concave pattern forming method according to any one of the first to tenth aspects, a highly-accurate minute convexo-concave pattern even in a nano size can be formed.
  • the minute convexo-concave pattern forming method and device in accordance with each of the above described aspects, when the mold on a side of transferring the minute convexo-concave pattern and the transfer substrate on a transferred side are peeled, the minute convexo-concave pattern transferred to the resist layer of the transfer substrate can be effectively prevented from being damaged. Therefore, a highly-accurate minute convexo-concave pattern even in a nano size can be formed. In particular, the minute convexo-concave pattern can be prevented from being damaged or deformed at the peel final end immediately before the peeling of the mold and the transfer substrate ends.
  • FIG. 1A is a process diagram of a nano imprint step of transferring a macro-convexo-concave pattern
  • FIG. 1B is a process diagram of a nano imprint step of transferring the macro-convexo-concave pattern
  • FIG. 1C is a process diagram of a nano imprint step of transferring the macro-convexo-concave pattern
  • FIG. 2A is an upper surface view of a combined body (work) obtained by a mold and a transfer substrate together in a transferring step;
  • FIG. 2B is a sectional view along 2 B- 2 B of FIG. 2A ;
  • FIG. 3A is an entire structural view (a perspective view) for describing an example of a minute convexo-concave pattern forming apparatus of the present invention
  • FIG. 3B is a drawing of a work holder portion of a minute convexo-concave pattern (a partial perspective cross sectional view along a 3 B- 3 B line of FIG. 3A );
  • FIG. 4 is an explanatory diagram describing a control system of the minute convexo-concave pattern forming device
  • FIG. 5 is a flowchart of processes of a peeling method in the present invention and a general peeling method
  • FIG. 6A is an explanatory diagram for describing a maximum bending amount
  • FIG. 6B is an explanatory diagram for describing a maximum bending amount
  • FIG. 7 is an explanatory diagram for describing a minute convexo-concave pattern of a mold for use in an example
  • FIG. 8 is an explanatory diagram of changes in load in a conventional general peeling method (without assist pressurization);
  • FIG. 9 is a peel force waveform analysis diagram in the peeling method in the present invention (with assist pressurization);
  • FIG. 10 is an explanatory diagram of changes in load in the peeling method in the present invention (with assist pressurization);
  • FIG. 11 is an explanatory diagram for describing a load behavior in a final peeling process in the peeling method in the present invention (with assist pressurization);
  • FIG. 12A is an explanatory diagram for describing the state of the minute convexo-concave pattern of a transfer substrate peeled with the conventional general peeling method
  • FIG. 12B is an explanatory diagram for describing the state of the minute convexo-concave pattern of the transfer substrate peeled with the conventional general peeling method.
  • FIG. 13 is an explanatory diagram for describing the state of the minute convexo-concave pattern of the transfer substrate peeled with the peeling method in the present invention.
  • a metal material is subjected to a three-dimensional stereoscopic process by using a semiconductor microfabrication technology to form a mold (a form) 10 including a minute convexo-concave pattern as illustrated in FIG. 1A .
  • an original plate may be formed by performing a molding process on a metal material, a pattern formed on the surface of the original plate may be transferred to a resin material to fabricate a rein stamper, and this stamper may be used as the mold 10 .
  • a material of the mold 10 any can be selected as appropriate according to the object, and a metal, quartz, resin, or the like can be suitably used.
  • Ni, Si or SiO 2 , Cu, Cr, Pt, or the like can be used, and, as a resin material, polyethylene terephthalate, polyethylene naphthalate, polycarbonate, fluororesin, or the like can be used.
  • a surface of a minute convexo-concave pattern 10 A of the fabricated mold 10 is preferably coated with a release layer.
  • the release layer is preferably formed on the surface of the minute convexo-concave pattern 10 A so that peeling can be made so as to prevent a failure due to stress at the time of peeling on a transfer interface between the mold 10 and a resist layer 12 after transferring and curing processes, which will be described further below.
  • a material of the release layer any material can be selected as appropriate as long as the material is suitable for the purpose of being easily attached and coupled to a mold 10 side and being less prone to be suctioned to a resist layer 12 side.
  • a fluorine-based resin having a low electronegativity is preferable.
  • the thickness of the release layer is preferably made as thin as possible because a too high thickness changes the minute convexo-concave pattern 10 A, and, specifically, the thickness is preferably 5 nm or less, and more preferably 3 nm or less.
  • a release layer As a method of forming a release layer, coating or vapor deposition of the material of the release layer can be applied. Furthermore, after the release layer is formed, it is preferable to increase adhesiveness to the mold 10 by baking or the like to improve the strength of the release layer itself.
  • a coating process, a transferring process, and a peeling process are performed to form a minute convexo-concave pattern 12 A on the resist layer 12 of a transfer substrate 14 .
  • a substrate 16 is coated with a resist fluid obtained by dissolving a resin material forming the resist layer 12 in a solvent to form the transfer substrate 14 having the resist layer 12 formed on the substrate 16 .
  • a resin material forming the resist layer 12 for example, a thermoplastic resin, thermosetting resin, and photo-curable resin can be preferably used.
  • a material of the substrate 16 for example, a glass substrate, Si substrate, or the like can be used.
  • any of the following methods can be suitably used.
  • the resist fluid is dropped by a dropping device such as an ink jet to an appropriate location on the substrate 16 , and is spread with fluidity of the resist fluid itself to be applied uniformly onto the substrate 16 .
  • the resist fluid is applied uniformly onto the substrate 16 .
  • the thickness of the resist layer 12 with which the substrate 16 is coated can be measured with, for example, an optical measurement method using an ellipsometer or the like or a stylus-type contact measurement scheme using a step gauge, an atom force microscope (AFM), or the like.
  • an optical measurement method using an ellipsometer or the like or a stylus-type contact measurement scheme using a step gauge, an atom force microscope (AFM), or the like.
  • AFM atom force microscope
  • the minute convexo-concave pattern 10 A of the mold 10 is transferred to the resist layer 12 of the transfer substrate 14 .
  • the minute convexo-concave pattern 10 A of the mold 10 is transferred to the resist layer 12 of the transfer substrate 14 .
  • it is required to change surrounding pressure conditions for forcible filling.
  • the following filling methods (1) to (2) can be suitably used.
  • the mold 10 is pressurized toward the resist layer 12 by a pressing machine or the like. In this case, by pressurizing or heating the resist layer 12 , the recessed parts of the minute convexo-concave pattern 10 A can be more easily filled with the resist fluid.
  • the mold 10 is placed on the resist layer 12 to be under a heating and pressure-reducing conditions. With this, air and air bubbles left in recessed parts of the minute convexo-concave pattern 10 A are removed, and thus the recessed parts are filled with the resist fluid.
  • FIG. 2A is an upper surface view of the work 20
  • FIG. 2B is a sectional view along 2 B- 2 B of FIG. 2A .
  • the work 20 is in a circular shape in the present embodiment, this is not meant to be restrictive, and the work may be in a rectangular shape, for example.
  • any of the following methods (1) to (3) can be suitably used.
  • FIG. 1 B illustrates an example in which the resist layer 12 is cured by applying curing light from the back surface of the transparent mold 10 allowing passage of light.
  • the resist layer 12 is cured by being cooled after transfer.
  • FIG. 1C illustrates an example of a general tensile peeling method of peeling the mold 10 and the transfer substrate 14 by fixing the transfer substrate 14 and pulling the mold 10 in a vertical direction upward.
  • the problem described above is solved by performing, as a peeling process, a first peeling process of pressurizing a substrate back surface side of the transfer substrate 14 with a peripheral part of the transfer substrate 14 being fixed to bent the transfer substrate 14 in a curved shape, thereby starting peeling of the transfer substrate 14 and the mold 10 ; and a second peeling process of gradually decreasing a pressure for pressurization on the substrate back surface side to act a bending resilient force on the transfer substrate 14 , thereby peeling a minute convexo-concave pattern 12 A part of the minute convexo-concave pattern 12 A of the transfer substrate 14 not peeled in the first peeling process.
  • a pressure for pressurization on the substrate back surface side of the transfer substrate 14 in the first and second peeling process described above is hereinafter referred to as an assist pressure.
  • the mold 10 moves in a direction perpendicular to a substrate surface of the transfer substrate 14 before bending.
  • This movement of the mold 10 may be made without using a moving and driving device for movement, and the mold 10 may be moved as following a bending force with which the transfer substrate 14 is bent. Alternatively, the movement may be made forcibly by a moving and driving device.
  • FIG. 3A is an entire structure view (a perspective view) illustrating an example of a peeling device 21 including a moving and driving device in the embodiment of the present invention
  • FIG. 3B is a sectional view (a partial perspective cross sectional view along a 3 B- 3 B line of FIG. 3A ) illustrating the state in which the work 20 is set at a work holder 22 .
  • the peeling device 21 is configured to have the work holder 22 , a pressurizing device 24 , and a moving and driving device 26 assembled to a device frame 30 .
  • struts 32 , 32 , . . . stand respectively at four corners of a rectangular base 31 , and a support plate 34 is provided to support the work holder 22 over the struts 32 .
  • a circular hole 34 A (refer to FIG. 4 ) is formed, and the work holder 22 is supported on the support plate 34 so as to go across the circular hole 34 A.
  • the work holder 22 mainly has a structure in combination of a disk-shaped upper plate 36 and a donut-shaped lower plate 38 having a circular hole 38 A formed at a center part, and, around the circular hole 38 A of the lower plate 38 , a substrate receiving surface 38 B receiving the transfer substrate 14 of the work 20 is formed. And, to perform the peeling process, the work 20 obtained by combining the mold 10 and the transfer substrate 14 is set at the work holder 22 . In this case, the transfer substrate 14 is placed on the substrate receiving surface 38 B with the mold 10 on a lower side and is then covered with the upper plate 36 so that an O ring 40 provided to an upper surface peripheral part of the transfer substrate 14 is crushed, thereby fixing the upper plate 36 and the lower plate 38 with a fixing member not illustrated. With this, the peripheral part of the transfer substrate 14 is fixed, and a pressurization space 42 in an airtight structure surrounded by an upper surface of the transfer substrate 14 , a lower surface of the upper plate 36 , and the O ring 40 is formed.
  • a pressurizing device 24 To this pressurization space 42 , compressed air is blown by a pressurizing device 24 .
  • a flow path 24 A is formed inside the upper plate 36 to let compressed air flow to the pressurization space 42 , and a blow port 24 B at a tip of the flow path 24 A is open to face the pressurization space 42 .
  • the flow path 24 A is connected with a piping 44 via a compression control mechanism 45 (refer to FIG. 4 ) to a compressor 47 .
  • the pressure control mechanism 45 has two functions of adjusting an amount of compressed air to be supplied from the compressor 47 to the pressurizing device 24 to adjust the pressure in the pressurization space 42 , and venting the compressed air from the pressurization space 42 to decrease the pressure of the pressurization space 42 . And, when compressed air is supplied to the pressurization space 42 , the substrate back surface side of the transfer substrate 14 is pressurized, and the transfer substrate 14 is bent in a curved shape (curved so as to project downward). Note that while the compressed air is supplied to the pressurization space 42 to bend the transfer substrate 14 in the present embodiment, a liquid can be supplied to the pressurization space 42 . Also, a method with a structure other than that of supplying air or fluid to the pressurization space 42 can be applied.
  • a solid substance (not illustrated) having an abutting surface with a predetermined curvature and many suction holes on the abutting surface is provided on the substrate back surface side of the transfer substrate 14 .
  • the transfer substrate 14 may be curved by causing the abutting surface of this solid substance on the transfer substrate 14 for suctioning.
  • the lower surface of the mold 10 protrudes to a lower surface side of the support plate 34 via the circular hole 38 A of the lower plate 38 and the circular hole 34 A of the support plate 34 .
  • This lower surface of the mold 10 is suctioned by a suction head 50 of the moving and driving device 26 , which will be described next.
  • the moving and driving device 26 includes the suction head 50 suctioning the lower surface of the mold 10 and an ascent/descent device 52 causing the suction head 50 to ascend or descend.
  • an ascent/descent device 52 causing the suction head 50 to ascend or descend.
  • FIG. 3A a detailed structure of the ascent/descent device 52 is not illustrated in FIG. 3A , in peeling of the minute convexo-concave pattern in a nano size, it is enough for the suction head 50 to normally have an ascending/descending stroke of 10 mm, and any device can be used as long as the device is capable of precise ascent/descent control over the ascending/descending stroke to this degree.
  • the moving and driving device 26 is provided with a load cell 54 ( FIG. 4 ) measuring a load applied to the transfer substrate 14 when the compressed air is supplied to the pressurization space 42 . That is, when compressed air is supplied to the pressurization space 42 to bend the transfer substrate 14 in a curved shape (curved so as to project downward), the load cell 54 is pressed by the bending force, and this pressure is measured by the load cell 54 as a load.
  • FIG. 4 is a schematic view of the pressure control mechanism 45 for the pressurizing device 24 , a suction control mechanism 53 for the suction head 50 , a temperature control mechanism 56 for the suction head 50 , and a movement control mechanism 57 for the moving and driving device 26 .
  • the piping 44 connecting the compressor 47 and the blow port 24 B inside the work holder 22 is provided with a solenoid valve 48 and an electro-pneumatic conversion regulator 46 , and these devices are controlled by a sequencer 55 based on the load measured by the load cell 54 .
  • the temperature control mechanism 56 is provided with a heater (not illustrated) incorporated in the suction head 50 and a temperature control device 56 A adjusting a heater temperature.
  • the temperature control device 56 A feeds the temperature state back to the sequencer 55 .
  • a vacuum flow path connecting the suction head 50 and a vacuum pump 58 is provided with a solenoid valve 60 and a pressure sensor 62 , and the solenoid valve 60 is controlled by the sequencer 55 .
  • the pressure sensor 62 is monitoring a vacuum achievement degree, and outputs to the sequencer 55 a signal indicating the presence or absence of suctioning. According to the output from the pressure sensor 62 , the sequencer 55 performs control for detecting suction abnormality or starting a peeling operation.
  • the movement control mechanism 57 is provided with a driver 64 driving the ascent/descent device 52 .
  • the driver 64 is controlled by the sequencer 55 based on the load measured by the load cell 54 .
  • a touch panel 66 is connected to the sequencer 55 , accepts inputs of various peeling condition parameters (such as a suction head driving speed, a driving stroke, and an assist pressure set value), accepts inputs of instructions for starting and stopping of the device, conducts an abnormal display, and performs others.
  • the load cell 54 is connected to the sequencer 55 via a load cell controller 68 .
  • FIG. 5 is a flowchart illustrating steps of the peeling method. Note that, as the peeling step of FIG. 5 , a selection can be made from a peeling step to which the peeling method according to the embodiment described above and a peeling step by general tensile peeling.
  • the work 20 is set at the work holder 22 (step S- 1 ).
  • the transfer substrate 14 is placed on the substrate receiving surface 38 B with the mold 10 on a lower side and is then covered with the upper plate 36 so that the O ring 40 (a peripheral part fixing member) provided to the upper surface peripheral part of the transfer substrate 14 is crushed, thereby fixing the upper plate 36 and the lower plate 38 with a fixing member (for example, a bolt and a nut) not illustrated.
  • a fixing member for example, a bolt and a nut
  • the set temperature of the suction head 50 is preferably within a range from a room temperature (for example, 20 degrees Celsius) to 60 degrees Celsius.
  • a room temperature for example, 20 degrees Celsius
  • resilience of the transfer substrate 14 becomes larger, and therefore the minute convexo-concave pattern 12 A of the transfer substrate 14 is less prone to be damaged when the transfer substrate 14 is bent in a curved shape. If the temperature exceeds 60 degrees Celsius, viscosity of the transfer substrate 14 is increased, and become less prone to be peeled.
  • step S- 6 the method with an assist pressure (YES) for peeling or the method without an assist pressure (NO) for peeling is selected based on a condition set in advance on the touch panel 66 .
  • YES is selected, and the procedure goes to the next step S- 7 .
  • step S- 7 an operation of sending compressed air to the pressurization space 42 of the work holder 22 is turned ON, thereby pressurizing the substrate back surface side of the transfer substrate 14 .
  • a pressure to cause bending in a curved shape projecting downward occurs to the transfer substrate 14 .
  • the suction head 50 is not moved yet, and therefore a compressed load is applied to the load cell 54 .
  • a maximum bending amount L is a bending amount L of the transfer substrate 14 when an assist pressure P is applied in a state of a transfer substrate carrier. Stroke settings in the first peeling process are required to satisfy the following two conditions.
  • the minute convexo-concave pattern 12 A formed on the outer peripheral part of the transfer substrate 14 due to bending of the transfer substrate 14 by the assist pressure P can be peeled away from the mold 10 .
  • the stroke settings in the first peeling process are preferably as small as possible within a range satisfying the condition of stroke settings in the first peeling process described above.
  • the assist pressure is preferably in a range of 0.02 MPa to 0.03 MPa.
  • the assist pressure is less than 0.02 MPa
  • the bending resilient force BF cannot be accepted.
  • the transfer substrate 14 is deformed at a dash from the curved shape to a flat shape to complete the peeling operation at a dash, and thus the minute convexo-concave pattern 12 A tends to be damaged or deformed.
  • the assist pressure is more than 0.03 MPa to become large, the transfer substrate 14 is excessively bent, and damage or deformation of the minute convexo-concave pattern 12 A tend to occur, and, at worst, the transfer substrate 14 itself is damaged.
  • the suction head 50 starts making a descending movement (step S- 10 ).
  • the transfer substrate 14 is bent by the assist pressure accumulated in the pressurization space 42 , and therefore the minute convexo-concave pattern 12 A formed on the outer peripheral part of the transfer substrate 14 is peeled away from the mold 10 by the bending of the transfer substrate 14 .
  • the first peeling process ends (refer to FIG. 6A ).
  • the moving speed of the suction head 50 is preferably 0.1 mm/second or less, and more preferably 0.05 mm/second or less.
  • the transfer substrate 14 is abruptly bent, and therefore the minute convexo-concave pattern 12 A on the outer peripheral part of the transfer substrate 14 to be peeled tends to be damaged or deformed.
  • the suction head 50 may move as following by the bending force with which the transfer substrate 14 is bent without providing the moving and driving device 26 for moving the suction head 50 , as described above.
  • the procedure goes to the next step S- 12 .
  • the procedure may immediately go to step S- 12 .
  • the procedure may go to step S- 12 after stopping or after a stop state continues for a predetermined time. With the stop for the predetermined time, the minute convexo-concave pattern 12 A peelable in the first peeling process can be reliably peeled.
  • a mechanism of stopping the descending movement of the suction head 50 a mechanical lock mechanism or a holding mechanism included in a driving system may be used.
  • step S- 12 air is gradually released from the pressurization space 42 , and reduction of the assist pressure P for pressurizing the substrate back surface side of the transfer substrate 14 starts. Then, when the assist pressure P is gradually decreased and the bending resilient force BF becomes larger than the assist pressure P, the minute convexo-concave pattern 12 A at the center part of the transfer substrate 14 not peeled in the first peeling process is peeled away from the mold 10 (refer to FIG. 6B ). Reduction of the assist pressure ends when the pressure of the pressurization space 42 returns to atmospheric pressure (step S- 13 ). With this, the second peeling process ends, and peeling of the mold 10 and the transfer substrate 14 is completed, and the mold 10 and the transfer substrate 14 are separated from each other.
  • step S- 14 the suction head 50 is retreated to a mechanical origin (step S- 14 ), a peeling stop complete buzzer sounds, and the automatic peeling operation ends (step S- 15 ).
  • the minute convexo-concave pattern 12 A at the center part of the transfer substrate 14 is not peeled at a dash, is gradually peeled at a slow peeling speed with a small peel force.
  • the minute convexo-concave pattern 12 A at the peel final end is coupled to the mold 10 . Therefore, if a large bending resilient force (peel force) is provided at a dash when peeling is completed, the minute convexo-concave pattern 12 A at the peel final end is damaged.
  • peel force peel force
  • peeling can be performed so as not to damage or deform the minute convexo-concave pattern 12 A.
  • the suction head may be cause to descend continuously while the assist pressure P is being gradually decreased to act the bending resilient force BF on the mold 10 and the transfer substrate 14 .
  • a peel force F is provided in a direction in which the mold 10 and the transfer substrate 14 are peeled away from each other.
  • the moving speed of the suction head is preferably at 0.1 mm/second or less, and more preferably at 0.05 mm/second or less.
  • the pressurizing force may be controlled based on an elapsed time from the start of pressurization. Also, control may be made based on a movement amount of the mold 10 at the start of pressurization, or control may be made based on a bending amount of the transfer substrate 14 from the start of pressurization. In these cases, it is required to find a correlation by performing a preliminary test in advance to set conditions.
  • step S- 6 when the general tensile peeling process is selected (NO) at step S- 6 , a load measurement by the load cell 54 starts (step S- 16 ), and also the suction head 50 is moved to descend (step S- 17 ), thereby causing the mold 10 and the transfer substrate 14 to be pulled away from each other. Then, the mold 10 and the transfer substrate 14 are peeled at a dash. After the peeling ends, the descending movement of the suction head 50 stops (step S- 18 ).
  • the mold 10 for nano imprint having a minute convexo-concave pattern in a nano size was brought into close contact with the transfer substrate 14 coated with the resist layer 12 in advance, thereby transferring the minute convexo-concave pattern to the resist layer 12 of the transfer substrate 14 .
  • operations were performed in the case of applying the peeling method according to the present embodiment to the peeling process after transfer and in the case of not applying the peeling method of the present embodiment, and the state of the minute convexo-concave pattern 12 A after peeling was observed.
  • each minute convexo-concave pattern 10 A has a section size with an L/S width of 2 ⁇ m and a height of 2 ⁇ m (an aspect ratio of 1) of a micro-texture. And, a surface where the minute convexo-concave patterns 10 A were formed was coated with a release liquid. Note that while only a plurality of line-shaped minute convexo-concave patterns are drawn in FIG. 7 , there are many pattern lines in a practical situation.
  • the transfer substrate 14 a disk-shaped quartz having a thickness of 0.5 mm and a diameter of 6 inches (150 mm) was used, and, as the resist layer 12 , a UV (ultraviolet) curable resin was coated. Note that the conditions of the mold 10 and the transfer substrate 14 described above were the same between a comparative example and the example.
  • the work 20 as a combined body obtained by combining the mold 10 and the transfer substrate 14 together after transfer was set at the work holder 22 of FIG. 3 . Then, general peeling steps S- 1 to S- 6 and steps S- 16 to S- 18 of FIG. 5 (the comparative example) and peeling steps S- 1 to S- 15 to which the present invention is applied (the example) were respectively performed.
  • FIG. 8 illustrates changes in load with time applied to the load cell 54 when the steps of the general tensile peeling method are performed.
  • the horizontal axis represents an elapsed time from the start of peeling to the end thereof, and the vertical axis represents a peeling load measured by the load cell 54 .
  • the descending movement speed of the suction head 50 was set at 0.05 mm/second, and the heating condition of the suction head 50 was set at 46 degrees Celsius.
  • the assist pressure (a supply pressure of compressed air) was set at 0.025 MPa, and the maximum bending amount was set at 1 mm.
  • the operation of reducing the assist pressure using an electro-pneumatic conversion regulator is better in view of reproducibility in a practical situation. In the present example, however, the operation was performed by manually rotating a regulator valve at a predetermined speed.
  • FIG. 9 is a peel force waveform analysis diagram with assist pressurization
  • FIG. 10 is a diagram of change in load actually measured by the load cell 54 .
  • the horizontal axis represents an elapsed time from the start of peeling to the end thereof, and the vertical axis represents a peeling load measured by the load cell 54 .
  • the load is abruptly decreased after the assist pressure is applied, because the pressurization space 42 of the work holder 22 is pressurized to cause the work 20 to press the load cell 54 , thereby applying a compressed load (a load oriented downward in FIG. 10 ) to the load cell 54 .
  • the assist pressure has reached the predetermined pressure (the pressure for achieving the maximum bending amount)
  • the suction head 50 is moved to descend, the transfer substrate 14 is bent in a curved shape, and the first peeling process starts with this bending.
  • the minute convexo-concave pattern 12 A on the outer peripheral part transfer substrate 14 is peeled.
  • a tensile load (a load oriented upward in FIG. 10 ) is applied to the load cell 54 .
  • the descending movement of the suction head 50 stops.
  • a portion of the upward load once flattened represents a point of the maximum bending amount L.
  • the bending resilient force BF is applied to the transfer substrate 14 .
  • the second peeling process starts, and the minute convexo-concave pattern 12 A at the center part of the transfer substrate 14 not peeled in the first peeling process is peeled away from the mold 10 with a small peel force at a slow peeling speed.
  • the minute convexo-concave pattern 12 A transferred to the resist layer 12 of the transfer substrate 14 can be effectively prevented from being damaged when the mold 10 and the transfer substrate 14 are peeled.
  • FIG. 11 illustrates an enlarged load behavior in the final peeling process immediately before the second peeling process is completed in FIG. 10 , in which a portion surrounded by a circle in FIG. 10 is enlarged.
  • tensile load applied to the minute convexo-concave pattern 12 A at the peel final end (the center of the transfer substrate) peeled in the final peeling process was 2 N.
  • the tensile load in the final peeling process in the general tensile peeling method illustrated in FIG. 8 (20 N) is decreased to 1/10.
  • FIG. 12A and FIG. 12B illustrate SEM (scanning electron microscope) photographs obtained by capturing the minute convexo-concave pattern 12 A of the transfer substrate 14 peeled with the general peeling method described above by using an electron microscope.
  • FIG. 13 illustrates the minute convexo-concave pattern 12 A of the transfer substrate 14 peeled with the peeling method of the present invention, which can be compared with that of FIG. 12A .
  • a projecting line in a line shape is not peeled at all, and the minute convexo-concave pattern 12 A has been precisely transferred.
  • pressure control mechanism 46 . . . electro-pneumatic conversion regulator, 47 . . . compressor, 48 . . . solenoid valve, 50 . . . suction head, 52 . . . ascent/descent machine, 53 . . . suction control mechanism, 56 . . . temperature control mechanism, 57 . . . movement control mechanism, 58 . . . vacuum pump, 60 . . . solenoid valve, 62 . . . pressure sensor, 64 . . . driver, 66 . . . touch panel, 68 . . . load cell controller

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JP6084055B2 (ja) * 2013-02-05 2017-02-22 東京応化工業株式会社 インプリントによるパターン形成方法
JP6029506B2 (ja) 2013-03-26 2016-11-24 富士フイルム株式会社 インプリント用下層膜形成組成物およびパターン形成方法
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